WO1996020786A1 - Catalyseur et procede pour epurer un gaz brule de fumigation - Google Patents

Catalyseur et procede pour epurer un gaz brule de fumigation Download PDF

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Publication number
WO1996020786A1
WO1996020786A1 PCT/JP1995/002749 JP9502749W WO9620786A1 WO 1996020786 A1 WO1996020786 A1 WO 1996020786A1 JP 9502749 W JP9502749 W JP 9502749W WO 9620786 A1 WO9620786 A1 WO 9620786A1
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Prior art keywords
catalyst
exhaust gas
fumigation
purifying
component
Prior art date
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PCT/JP1995/002749
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English (en)
Japanese (ja)
Inventor
Kunio Sano
Kazuyoshi Nishikawa
Kazunori Yoshino
Kazumi Okuhara
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Nippon Shokubai Co., Ltd.
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Application filed by Nippon Shokubai Co., Ltd. filed Critical Nippon Shokubai Co., Ltd.
Priority to DE69527305T priority Critical patent/DE69527305D1/de
Priority to EP95942303A priority patent/EP0801979B1/fr
Priority to US08/860,464 priority patent/US6051198A/en
Publication of WO1996020786A1 publication Critical patent/WO1996020786A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/648—Vanadium, niobium or tantalum or polonium
    • B01J23/6482—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • B01J35/60—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01J35/633—
    • B01J35/635—
    • B01J35/647—
    • B01J35/651—

Definitions

  • the present invention relates to a catalyst for detoxifying flue gas after being used for disinfecting and killing food such as cereals and fruits and vegetables, or timber and soil, and using such a catalyst. And particularly to a method for purifying fumigation exhaust gas by efficiently decomposing explosive components such as methyl bromide and chloropicrin in the furnace exhaust gas.
  • the present invention relates to a catalyst, a method for purifying flue gas, and the like.
  • the fumigation method is a method of controlling pests by filling an enclosed space with a gaseous chemical (fumigant), and is mainly implemented as an epidemic control measure for imported food such as cereals and fruits and vegetables, and wood. It is also used for sterilization and insecticide of soil for greenhouse cultivation.
  • the fumigation gas used in such a baking method contains an organic halogen compound such as methyl bromide-picopenic acid as a furnace component. Are used in extremely large quantities.
  • the fumigation flue gas containing a large amount of the organic halogen compound as described above is actually released to the atmosphere without detoxification after use.
  • the ozone layer which plays an important role in the global environment, has been destroyed by the above-mentioned organohalogen compounds.
  • Use regulations are becoming stricter, and a method for purifying steam exhaust gas by decomposing organic halides such as methyl bromide and chloropicrin contained in explosive fumes gas with high efficiency and low cost is established. Is in a hurry. «Methods for effectively decomposing the fumigation components in steam exhaust gas have been studied for some time, but under the above circumstances, they have been studied from various angles before. .
  • the concentration of fumigation components in explosive flue gas is, for example, about
  • the chemical solution absorption method requires special chemicals and generates a large amount of wastewater, which requires secondary treatment, and is not practical due to the low removal efficiency. .
  • a catalytic oxidation method for example, there is a method disclosed in Japanese Patent Application Laid-Open No. 3-289973.
  • an organic halogen compound can be oxidatively decomposed by contact with a composite oxide catalyst, a large amount Carbon monoxide may be generated, and harmful phosgene and bromophosgene may be generated by the reaction between carbon monoxide and halogen.
  • problems such as the necessity of arranging an oxidation catalyst at a later stage.
  • activated carbon is generally used as an adsorbent.
  • the amount of the adsorbent used may be small, and the breakthrough time Is also longer.
  • the breakthrough time becomes short. To deal with this, an extremely large amount of adsorbent is required. Is required.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to use a fumigation exhaust gas purification catalyst capable of purifying fumigation exhaust gas economically and with high efficiency, and using the catalyst.
  • An object of the present invention is to provide a method for purifying flue gas.
  • the present invention relates to a catalyst for purifying furnace exhaust gas, wherein a catalyst A component is a metal oxide or a metal oxide of at least one metal selected from the group consisting of Ti, Si and Zr.
  • a catalyst C component one or more metal elements selected from the group consisting of Pd, Pt, Rh, Ru and Au, or an oxide thereof, or Z or a catalyst It is also effective to include, as the D component, an oxide of one or more metals selected from the group consisting of Ce, Pr, Nd, Mo, and Sn.
  • the method of the present invention comprises adding a fumigation
  • a fumigation is a method for purifying furnace exhaust gas, which has an essential point in that the exhaust gas is brought into contact to decompose the steam component in the exhaust gas.
  • the above method is particularly effective when the explosive component is methyl bromide and / or chloropicrin.
  • the following method is used: IAdsorbing the I vapor component in the furnace exhaust gas to the adsorbent to remove the explosive component from the furnace exhaust gas,
  • An example is a configuration in which the explosive component is desorbed, and the desorbed fumigant component is brought into contact with the above-described explosive exhaust gas purifying catalyst to be decomposed.
  • the adsorbent used at this time include one or more adsorbents selected from the group consisting of granular activated carbon, fibrous activated carbon, granular zeolite, and fibrous zeolite.
  • FIG. 1 is a schematic explanatory view showing an example of the configuration of a steam exhaust gas purifying facility for carrying out the method of the present invention.
  • FIG. 2 is a schematic explanatory view showing one configuration example of a rotary adsorption device.
  • the fumigation flue gas is exhausted by sending air into the furnace steaming system. Therefore, as described above, the initial emission concentration of the fumigant component ( «fumigant) contained in the fumigation flue gas is extremely high, about 1% by volume. Concentration, which rapidly decreases with the discharge time (2-4 hours) and reaches several ppm at the end of the discharge operation. Rapidly changing over such a wide range It is difficult to efficiently remove explosives such as methyl bromide, etc., produced by the present inventors.First, the present inventors studied problems in a high concentration range, and conducted intensive research on means for solving this problem. Stacked.
  • the catalyst ⁇ component is a metal oxide of at least one metal selected from the group consisting of Ti, Si, and Zr or a composite oxide containing two or more metals, and a catalyst B component.
  • Te, V, C u f W and a catalyst containing an oxide containing one or more metals selected from the group consisting of C r, and an average pore diameter of 0.0 1 0-0 of the catalyst 070 / m, a total pore volume of 0.30 to 0.6 Om 1 Zg, and a specific surface area of 50 to 200 m 2 / g were found to be extremely effective, and the present invention was completed.
  • the present inventors have also studied the problems in the low concentration range, and have conducted intensive research on means for solving this problem.
  • the original fumigation component is 1 00 0
  • the present inventors have also studied from the viewpoint of solving such inconveniences.
  • the fumigation component is adsorbed by an adsorbent made of activated carbon zeolite, etc., and the fumigation component is once removed from the flue gas.
  • hot air of 1 to 5 to 15 of exhaust gas is sent to the adsorbent.
  • the adsorbed fumigation component is desorbed, then introduced into a purification device filled with a catalyst to oxidatively decompose, and then, if necessary, heat removed by a heat exchanger.
  • the idea was that after cleaning and removing the acidic gas, it should be released to the outside air.
  • the adsorbent used at this time there can be mentioned various types such as granular activated carbon, fibrous activated carbon, granular zeolite, fibrous zeolite, and these can be used alone or in combination of two or more.
  • the shape of the adsorbent is not limited, and in addition to the above-mentioned granular and fibrous shapes, a honeycomb shape obtained by integrally molding can be used.
  • fumigation exhaust gas purification equipment filled with catalyst and adsorbent
  • the fumigation flue gas is directly introduced into the purification facility filled with the catalyst to purify the gas.
  • the degassing component is desorbed from the adsorbent by hot air with an exhaust gas volume of 15 to 115, and the concentrated desorbed gas is filled with a catalyst. And purify it.
  • the scale is relatively small, like fumigation of greenhouse soil.
  • a movable adsorber may be provided, and the steam exhaust gas may be adsorbed by the adsorber as needed.
  • a purification facility filled with a catalyst is installed jointly by an association or a regional group, and the adsorber whose adsorption has been completed in each house is installed in the place where the purification facility is installed.
  • the catalyst of the present invention comprises at least a catalyst A component and a catalyst B component.
  • the catalyst A component is at least one kind selected from the group consisting of Ti, Si and Zr. It is a metal oxide of a metal or a composite oxide containing two or more metals. This composite oxide is a solid acid and has an excellent dehalogenating effect from burning components such as methyl bromide and chloropicrin. It also has excellent characteristics and excellent selectivity for hydrogen halide generated by the reaction between halogen and hydrogen.
  • the catalyst B component constituting the catalyst of the present invention contains an oxide containing at least one metal selected from the group consisting of V, Cu, W and Cr.
  • the component B improves the properties of the composite oxide (catalyst A component), and in particular enables dehalogenation and hydrogen halide generation at lower temperature conditions.
  • the catalyst component may be a mixture of the above metal oxides or a composite oxide.
  • the catalyst used in the present invention contains at least the catalyst A component and the catalyst B component. It is also effective to contain at least one kind of gold) B element purple or an oxide thereof selected from the group consisting of Pd, Pt, Rh, Ru and Au.
  • the catalyst C component has an effect of suppressing the generation of harmful substances such as carbon monoxide, phosgene, and by-product organic halogen compounds, and increasing the complete oxidation rate.
  • the catalyst D component is added to improve the activity and heat resistance of the catalyst A component and the catalyst B component.
  • the ratio of each of the catalyst components A to D in the catalyst of the present invention is not particularly limited, but when the catalyst components A and B are used, at least the catalyst A component is 75 to 9 with respect to the entire catalyst component. It is preferably about 8% by weight. That is, when the content of the catalyst A is less than 75% by weight, the formability of the catalyst is deteriorated, which is not preferable. When it exceeds 98% by weight, the catalyst activity is lowered, which is not preferable. When the catalyst C component is contained, it is preferable that the content of the C component is about 0.01 to 10% by weight based on the total weight of the catalyst component (A + B). When the catalyst further contains a catalyst component, this component D is a catalyst component.
  • the catalyst of the present invention satisfies the above components, and further has an average pore diameter of 0.010 to 0.070 m, a total pore volume of 0.3 to 0.60 m 1 / . g specific surface area: it is necessary to satisfy the 5 0-2 0 each requirement of Om 2. That is, the present inventors examined the influence of the form of the catalyst on the furnace exhaust gas, and found that if the above requirements were satisfied, the catalyst would be oxidatively decomposed to fumigant components such as methyl bromide-micro-mouthed picrine. Demonstrate excellent performance We found that we did.
  • each average pore diameter 0. 0 1 5 ⁇ 0. 035 im , total pore volume:. 0. 40 ⁇ 0 50m l Zg, specific surface area: 80 ⁇ 1 60m 2 Zg It is.
  • the average pore diameter means the average diameter calculated from the pore distribution measured by the mercury intrusion method, and the total pore volume is the total volume of the pores measured by the mercury intrusion method. It means the meaning, including the carrier.
  • the partial pressure of halogens (Br, C1, etc.) generated during decomposition on the catalyst increases, and they are adsorbed at the active sites of the catalyst.
  • the active sites of the catalyst are covered with these halogens, adsorption of oxygen molecules required for oxidative decomposition is inhibited, and the activity of the catalyst is reduced. Therefore, in order to maintain the activity of the catalyst, the generated halogen must be quickly released from the catalytically active site.
  • the shape of the catalyst according to the present invention may be any of a spherical shape, a pellet shape, and a honeycomb shape, but is preferably a honeycomb type formed of an integrally molded product. The reason is as follows.
  • the aperture of the catalyst can be freely selected by selecting a molding die, and the catalyst can be molded to a length of about 1 m or less. Therefore, by filling the catalyst with such a shape, dusts that coexist in the gas pass through the straight pipe cell of the catalyst promptly and can be prevented from accumulating in the catalyst layer.
  • the space velocity of the gas when treating the steam exhaust gas with the catalyst is preferably about 1,000 to 20,000 hr- ', more preferably about 2000 to 1000 hr-',
  • the catalyst temperature at this time is 200-500.
  • C is preferred, more preferably about 250-450.
  • FIG. 1 is a schematic explanatory view showing an example of the configuration of a fumigation flue gas purifying facility for carrying out the method of the present invention, in which 1 is a fumigation silo, 2 is a blower, 3 is a heat exchanger, and 4 is A heater, 5 is a reactor, 6 is an alkaline solution storage tank, 7 is a pump, 8 is an alkaline scrubber, 9 is a circulation pump, and 10 is a fumigation exhaust gas purification catalyst.
  • a reactor 10 is filled with a fumigation flue gas purification catalyst 10 and the temperature is controlled by a temperature indicator controller (TIC) in the reactor 5.
  • TIC temperature indicator controller
  • Fig. 2 shows an example of the configuration of a rotary suction device, but is a schematic explanatory diagram.
  • 11 denotes a regenerative blower
  • 12 denotes a heater
  • 13 denotes a rotatable honeycomb adsorbent.
  • the fumigation exhaust gas A from the explosive silo is introduced into the honeycomb-type adsorbent 13 to adsorb the fumigation components, and the residual fumigation components are adsorbed. Is released as purified gas B.
  • the explosive components adsorbed on the honeycomb-shaped adsorbent 13 are desorbed by introducing the hot air heated by the heater 12 into the honeycomb-shaped adsorbent 13 by the regenerative blower 11 and then desorbing the catalyst. It is sent to the purification device (Reactor 5) to be oxidized and decomposed.
  • C indicates steam, which is a heat source of the heater 12.
  • an electric heater can be used as a heat source.
  • the discharged flue gas is introduced into the explosion fume exhaust gas purification equipment shown in Fig. Analysis was performed.
  • the steam exhaust gas-purifying catalyst 10 filled in the reactor 5 was prepared according to the following procedure.
  • First binary composite oxide comprising titanium emissions and silicon - was prepared by (T i 0 2 S i 0 2) to the following methods.
  • T i 0 2 obtained in this way - after ⁇ washed with water S i 02 gel was dried 1 0 hour at 200 ° C, and calcined 3 hours at 500.
  • fired body-1 8.4 kg of oxalic acid was dissolved in 18 liters of water, and 4.28 kg of ammonium metavanadate was added thereto. 1.5 kg was added, mixed and kneaded well with a kneader. Further, after kneading while adding an appropriate amount of water, it was extruded into a honeycomb shape having an outer shape of 150 mm square, a hole diameter (equivalent diameter of a through hole): 2.8 mm, and a porosity: 70%. 0 e was dried for 6 hours in C, and an atmosphere whose oxygen concentration has been adjusted to less than 1 5%, and the molded body was fired for 6 hours at 4 5 0 e C. The molded body thus obtained is hereinafter referred to as "fired body-1".
  • the obtained catalyst for purifying fumigation exhaust gas is charged into the reactor 5 shown in FIG. 1, and the exhaust gas from the fumigation rhinoceros 1 is pressurized by the blower 2, and is heated to a predetermined temperature by the heat exchanger 3 and the heater 4. , And was oxidatively decomposed by the fumigation exhaust gas purifying catalyst filled in the reactor 5.
  • the exhaust gas oxidatively decomposed in the reactor 5 is then cooled down through the heat exchanger 3 and then introduced below the packed tower of the alkaline scrubber 8, where it is sprayed and supplied from above the packed tower PH 9 to 11 Aqueous solution of caustic soda (flow rate: 3m 3 Zhr) and released to the outside of the system.
  • the other processing conditions at this time were set as follows.
  • gas analysis was performed over time for 2 hours to measure the purification rate.
  • the gas analysis items were methyl bromide, hydrogen bromide and carbon monoxide.
  • the results of gas analysis are shown in Table 1 below, and it can be seen that fumigation flue gas was efficiently purified over a long period of time.
  • the exhaust gas two hours after the start of the discharge from the combustion silo 1 was introduced into the rotary adsorption / desorption device shown in Fig. 2 and continuously adsorbed, while the exhaust gas was kept at 130 ° Hot air heated to C was blown into the desorption zone of the honeycomb structure.
  • the honeycomb structure was formed by integrally forming fibrous activated carbon, and the adsorption zone, the desorption zone, and the cooling zone were all formed by 13 pieces.
  • the exhaust gas thus desorbed was led to the flue gas purification equipment shown in FIG. 1, and the gas was analyzed in the same manner as in Example 1.
  • the processing conditions at this time were set as follows.
  • Reactor inlet temperature 300 ° C
  • Example 1 a powder made of titanium oxide was prepared according to the method of Example 1 except that no snowtex was used. Using this titanium oxide, it was extruded into a lattice-shaped honeycomb type having an outer shape of 80 mm square, a hole diameter of 2.8 mm, and a porosity of 70% according to the method of Example 1, followed by drying and firing. Thus, “fired body 1 2” was obtained.
  • the catalyst obtained by impregnating the thus-obtained “fired body 1 2” with palladium was obtained.
  • Example 2 The same catalyst as in Example 1 was prepared.
  • the time T i 0 2 - S i 0 2 double coupling oxide: V 2 0 5: P d 8 9. 3: 1 0. 0: a 0.7, average pore diameter: 0. 0 2 3 m
  • the total pore volume was 0.45 ml Z g, and the BET specific surface area was 110 m 2 / g.
  • a catalyst was prepared by the following method. 0.7 liters of monoethanolamine are mixed with 7 liters of water, and 1.0 kg of ammonium paratungstate is added and dissolved, and then 1.1 kg of ammonium metavanadate is dissolved. Make a homogeneous solution. Further, 16 kg of the above TS-1 powder was added to this solution, mixed well with water in a kneader, mixed and kneaded, and then extruded with an extruder to form an outer shape of 80 mm square, 2.8 mm hole diameter, and opened a hole. Extrusion into a 70% lattice-shaped honeycomb mold, drying and firing. Thus, “fired body one 3” was obtained.
  • Catalyst No. 4 was obtained in the same manner as in the preparation of Catalyst No. 3 except that 0.5 kg of starch as a molding aid was added to obtain a molded product.
  • the composition of the obtained catalyst was the same as that of the catalyst No. 3, and the average pore diameter was 0.06 m, the total pore volume was 0.6 m 1 Zg, and the BET specific surface area was 180 m 2. g
  • 20% of the powder (TS-1) obtained in Example 1 contains 0.886 kg of ammonium metavanadate and 1.79 kg of ammonium paratungstate 10% aqueous solution of 10% monoethanolamine 12 kg, then add »powder as a molding aid, mix and knead with a kneader, and then use an extruder to form a 150 mm square, opening
  • Catalyst No. 7 was obtained in the same manner as in the preparation of catalyst No. 5, except that cerium nitrate was used instead of copper nitrate.
  • Catalyst No. 8 was obtained in the same manner as in the preparation of catalyst No. 5, except that neodymium nitrate was used instead of copper nitrate.
  • Catalyst No. 9 was obtained in the same manner as in the preparation of Catalyst No. 5 except that praseodymium nitrate was used instead of copper nitrate.
  • Catalyst No. 10 was obtained in the same manner as in the preparation of catalyst No. 5 except that a mixed aqueous solution of copper nitrate and chloroplatinic acid was used instead of using a mixed aqueous solution of nitric acid pot and palladium nitrate.
  • composition of the obtained powder, oxides and to T i 0 2: Z r 02 4: 1 (molar ratio), from the diffraction chart of the X-ray T i 0 2 and Z r 0 2 No distinctive peak was observed, and it was confirmed from a broad diffraction peak that the oxide was a composite oxide containing Ti and Zr having an amorphous microstructure.
  • a ternary composite oxide containing Ti, Si and Zr was prepared by the following procedure. As except that further addition of oxide chloride, zirconium (Z r OC 1 2 ⁇ 8 H 2 0) First Z r source, ternary complex oxide containing T i, S i and Z r according to the method of Example 1 Powder was prepared.
  • T i: S i: Z r 2 0: 4: a l (molar ratio), from the diffraction chart of X-ray T i 0 2, S i 0 2 and Z r 0 2 apparent intrinsic peak was not observed, T i having an amorphous microstructure from the blow-de diffraction peak, be a composite oxide containing S i and Z r was confirmed.
  • a honeycomb catalyst was obtained in the same manner as in the preparation method of Catalyst No. 5.
  • a catalyst was obtained in the same manner as in the preparation of catalyst No. 5, except that an aqueous solution of copper nitrate was used instead of using an aqueous solution of a mixture of copper nitrate and palladium nitrate.
  • TS-1 powder obtained in Example 1
  • 12 liters of water and antibacterial powder were added to the mixture, kneaded with a kneader, and further kneaded while adding an appropriate amount of water.
  • the extruder was used to form a honeycomb with an outer shape of 150 mm square, a mesh size of 2.8 mm, a wall thickness of 0.5 mm, and a length of 500 mm. Then, after drying in 8 0, under an air atmosphere, subjected to 5 hours firing at 4 5 0 e C, to obtain a "fired one 5".
  • the resulting fired body one 5, the average pore diameter: 0. 0 6 m, total pore volume: 0. 7 m 1 g, BET specific surface area: was 2 1 0 m 2.
  • a cordierite carrier consisting of 210 cells Z in
  • Catalyst bed inlet temperature 250. C, 2 7 5. C, 300 ° C
  • ADVANTAGE OF THE INVENTION This invention is comprised as mentioned above and can implement
  • a method for purification can be established.

Abstract

L'invention concerne un catalyseur pour épurer un gaz brûlé de fumigation, comportant un constituant A contenant un oxyde métallique d'au moins un métal choisi dans le groupe composé de Ti, Si et Zr ou bien un oxyde composite d'au moins deux métaux dudit groupe, et un constituant B contenant un oxyde d'au moins un métal choisi dans le groupe composé de V, Cu, W et Cr. Ce catalyseur présente un diamètre moyen de pore compris entre 0,010 et 0,070 νm, un volume de pore compris entre 0,30 et 0,60 ml/g, et une surface spécifique comprise entre 50 et 200 m2/g. Ce catalyseur permet une épuration économique et extrêmement efficace d'un gaz brûlé de fumigation.
PCT/JP1995/002749 1995-01-05 1995-12-27 Catalyseur et procede pour epurer un gaz brule de fumigation WO1996020786A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE69527305T DE69527305D1 (de) 1995-01-05 1995-12-27 Katalysator und methode zur reinigung von begasungsabgas
EP95942303A EP0801979B1 (fr) 1995-01-05 1995-12-27 Catalyseur et procede pour epurer un gaz brule de fumigation
US08/860,464 US6051198A (en) 1995-01-05 1995-12-27 Catalyst for purifying fumigation exhaust gases and a method of purifying fumigation exhaust gases

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP37195 1995-01-05
JP7/000371 1995-01-05
JP33190595 1995-12-20
JP7/331905 1995-12-20
JP33726795A JP3230427B2 (ja) 1995-01-05 1995-12-25 燻蒸排ガス浄化用触媒および燻蒸排ガスの浄化方法
JP7/337267 1995-12-25

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WO1996020786A1 true WO1996020786A1 (fr) 1996-07-11

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EP (1) EP0801979B1 (fr)
JP (1) JP3230427B2 (fr)
DE (1) DE69527305D1 (fr)
WO (1) WO1996020786A1 (fr)

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US10792647B2 (en) * 2009-04-21 2020-10-06 Johnson Matthey Public Limited Company Base metal catalysts for the oxidation of carbon monoxide and volatile organic compounds
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DE69527305D1 (de) 2002-08-08
JP3230427B2 (ja) 2001-11-19
JPH09225301A (ja) 1997-09-02
EP0801979B1 (fr) 2002-07-03
EP0801979A1 (fr) 1997-10-22
EP0801979A4 (fr) 1999-06-02
US6051198A (en) 2000-04-18

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